Cyclododecadienone derivatives as perfuming ingredients

ABSTRACT

The present invention relates to compounds of formula 
     
       
         
         
             
             
         
       
         
         
           
             wherein one R group is a hydrogen atom and the other is a hydrogen atom or a C 1-3  alkyl group; and 
             each carbon-carbon double bond of said compound, independently from each other, can be in a configuration Z or E or a mixture thereof;
 
which are useful perfuming ingredients.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/126,484 filed Dec. 16, 2013, which is the 371 filing of Internationalapplication no. PCT/EP2012/061554 filed Jun. 18, 2012, which claimspriority to European application no. 11170895.4 filed Jun. 22, 2011, theentire content of each of which is incorporated herein by referencethereto.

TECHNICAL FIELD

The present invention relates to the field of perfumery. Moreparticularly, it concerns the use as perfuming ingredient of derivativesof formula (I) as defined below. The present invention also comprisesthe composition wherein the invention's compound is part of a perfumingcomposition or of a perfuming consumer product.

PRIOR ART

To the best of our knowledge, in general terms 4,8-cyclododecadien-1-oneis a known compound which has been described in the literature, but onlyas chemical intermediate. For instance, one may cite EP 965575 whereinis disclosed a 87/12 mixture of (Z,E)-4,8-cyclododecadien-1-one and(E,Z)-4,8-cyclododecadien-1-one as starting material for the preparationof 1-(4,8-cyclododecadien)-2-methyl-1-propanone as perfuming ingredient.One may also cite US 2010/0190869 wherein 4,8-cyclododecadien-1-one isobtained as intermediate in the synthesis of perfuming aldehydes.However, these prior art documents do not report or suggest anyorganoleptic properties of the present invention's mixture of formula(I), or any use of said compounds in the field of perfumery.

Document U.S. Pat. No. 4,885,397 also discloses the preparation interalia of 4,8-cyclododecadien-1-one, as intermediate for the preparationof a number of other chemicals. Said document states clearly that onlythe C₁₅₋₁₇ ketones are useful as perfuming ingredient, to the contraryof what has been found in the present invention.

To the best of our knowledge, the compounds of formula (I), wherein A isother than a carbonyl, are not reported in the literature.

The perfumery industry knows cyclododec-2-enone as perfuming ingredientto impart patchouli oil notes (e.g. EP 115582), but this compoundpossesses a significantly different skeleton (i.e. the macrocyclecomprises a conjugated enone functionality) and odor from the one of thepresent invention. The closest known analogues of the invention'scompounds are 5,9-cyclododecadien-1-ol (see U.S. Pat. No. 3,128,304) orsome a alkoxy cyclododecadienones (see U.S. Pat. No. 4,990,495) but onceagain these compounds are significantly different (an alcohol orα-alkoxy-ketone versus a ketone) and have different odors as discussedbelow. Further below in Table 1 are highlighted the differences betweenthe invention's compounds and the prior art compounds.

These prior art documents do not report or suggest any organolepticproperties of the compounds of formula (I), and do not report or suggestany use of said compounds in the field of perfumery.

DESCRIPTION OF THE INVENTION

We have now surprisingly discovered that a 4,8-cyclododecadien-1-onederivative of

-   -   wherein one R group is a hydrogen atom and the other is a        hydrogen atom or a C₁₋₃ alkyl group; and    -   each carbon-carbon double bond of said compound, independently        from each other, can be in a configuration Z or E or a mixture        thereof;        can be used as perfuming ingredient, for instance to impart odor        notes of the woody type with aromatic, musky, and/or earthy        type.

For the sake of clarity, by the expression “a compound of formula (I) .. . each carbon-carbon double bond of said compound, independently fromeach other, can be in a configuration Z or E or a mixture thereof”, itis meant also a composition of matter comprising the various (E,E),(E,Z) or (Z,E) and (Z,Z) isomers of 4,8-cyclododecadien-1-one,12-methylcyclododeca-4,8-dienone and/or 2-methylcyclododeca-4,8-dienone.

According to any one of the above embodiments of the invention, one Rgroup is a hydrogen atom and the other is a hydrogen atom or a methyl orethyl group. In particular both R represent a hydrogen atom.

For the sake of clarity, by the expression “each carbon-carbon doublebond of said compound, independently from each other, can be in aconfiguration Z or E or a mixture thereof” it is meant the normalmeaning in the art, i.e. that said compound (I) can be in the form of anessentially pure stereoisomer (i.e. the (4E,8E) one) or in the form of amixture of stereoisomers, e.g. in a mixture comprising the stereoisomers(4E,8E), (4Z,8E) and (4E,8Z) in various w/w ratios.

In particular, the invention's compound can be in the form of a mixturecontaining predominantly the stereoisomers (4E,8E), (4Z,8E) and (4E,8Z),the remaining being essentially the (4Z,8Z) stereoisomer. In such acase, one may define a w/w ratio (4E,8E)/[(4Z,8E)+(4E,8Z)] for suchmixture of stereoisomers (also referred to as the (E,E)/((E,Z) ratio).According to a particular aspect of said embodiment, the compound (I) isin the form of a mixture of stereoisomers having a (E,E)/((E,Z) ratiocomprised between 20/80 and 1/99. According to said embodiment, saidmixture of stereoisomers has a (E,E)/((E,Z) ratio comprised between15/85 and 2/98.

Alternatively said compound (I) is in the form of a mixture ofstereoisomers having a (E,E)/((E,Z) ratio comprised between 80/20 and99.5/0.5. According to said embodiment, said mixture of stereoisomershas a (E,E)/((E,Z) ratio comprised between 90/10 and 99/1.

For the sake of clarity, by the expression “predominantly” it is meantthat the mentioned stereoisomer or mixture of stereoisomers representsmore than 90% of said compound (I), the remaining being obviously in theform of the other isomers.

As specific examples of the invention's compounds, one may cite, asnon-limiting example, 4,8-cyclododecadien-1-one in the form of a mixturecomprising about 99% w/w of (4E,8E)-4,8-cyclododecadien-1-one and about1% w/w of the (4Z,8E)-4,8-cyclododecadien-1-one and(4E,8Z)-4,8-cyclododecadien-1-one stereoisomer (i.e. a4,8-cyclododecadien-1-one in the form of a (E,E)/(E,Z) mixture 99/1 w/w,and also herein after referred to as “compound 1”). Said compound 1possesses a unique odor having a variety of notes. In particular, saidcompound displays a woody/pin character as well as dry, musky andvetiver/earthy facets. The pin note is not terpenic but slightlyaromatic, while the musky note reminds clearly of the nitro-musk notesby its powdery, sweet and earthy aspects.

As other example, one may cite 4,8-cyclododecadien-1-one in the form ofa mixture comprising at least 90% w/w of(4E,8Z)-4,8-cyclododecadien-1-one and (4Z,8E)-4,8-cyclododecadien-1-onestereoisomers and about 5% w/w of the (4E,8E)-4,8-cyclododecadien-1-onestereoisomer (i.e. a 4,8-cyclododecadien-1-one in the form of a(E,E)/(E,Z) mixture of below 5/90 w/w, and also herein after referred toas “compound 2”). Said compound 2 has an odor similar to the one of theabove described mixture but distinguishes itself by having a green notetoo and also by being more vetyver/earthy and aromatic, of the cardamomtype.

These two ketones blend very favorably with any other musks or woodingredients to impart a unique and unknown tonality by imparting anastonishing warmness and a richness of the fragrance.

As other specific, but non-limiting, examples of the invention'scompounds, one may cite the following ones in Table 1:

TABLE 1 Invention's compounds and their odor properties and prior artcompounds Compound structure and name Odor notes

  4,8-cyclododecadien-1-one in the form of a (E, E)/(E, Z) mixtureWoody, musky/ aromatic as described above. No aldehyde notes.

  (4E, 8E)-12-methylcyclododeca-4,8-dienone Woody, musky/ aromatic. Verysimilar to 4,8-cyclodo- decadien-1-one. No aldehyde notes.

  (4E, 8Z)-12-methylcyclododeca-4,8-dienone Woody, musky/ aromatic. Verysimilar to 4,8-cyclodo- decadien-1-one but slightly weaker. No aldehydenotes.

  (4Z, 8E)-12-methylcyclododeca-4,8-dienone Woody, musky/ aromatic. Verysimilar to 4,8-cyclodo- decadien-1-one but slightly weaker. No aldehydenotes.

  Mixture containing the various (Z, E) and (E, E) of isomers12-methylcyclododeca-4,8- dienone and 2-methylcyclodeca-4,8- dienoneWoody, musky/ aromatic. Very similar to 4,8-cyclodo- decadien-1-one butslightly weaker and more woody. No aldehyde notes.

  Cyclodec-2-en-1-one (see EP 115582) Patchouli oil, no musk or aromaticnotes.

  5,9-cyclododecdien-1-ol (see U.S. Pat. No. 3,128,304) Natural amber,no musk or aromatic notes.

  (see U.S. Pat. No. 4,990,495) All have aldehydic notes. No musky odor.

According to a particular embodiment of the invention, the compounds offormula (I) are (4E,8E)-4,8-cyclododecadien-1-one,(4Z,8E)-4,8-cyclododecadien-1-one, (4E,8Z)-4,8-cyclododecadien-1-one,(4E,8E)-12-methylcyclododeca-4,8-dienone,(4E,8Z)-12-methylcyclododeca-4,8-dienone,(4Z,8E)-12-methylcyclododeca-4,8-dienone,2-methylcyclododeca-4,8-dienone and the mixtures thereof.

When the odor of the invention's compounds is compared with that of theprior art compounds, then the invention's compounds distinguishthemselves by having a woody, aromatic and/or musky character and bylacking, or not possessing significant aldehyde notes, which arecharacteristic of some of the prior art compounds. Said differences lendthe invention's compounds and the prior art compounds to be eachsuitable for different uses, i.e. to impart different organolepticimpressions.

The compounds of formula (I) as above described are novel compounds andtherefore also an object of the present invention.

As mentioned above, the invention concerns the use of a compound offormula (I) as perfuming ingredient. In other words, it concerns amethod to confer, enhance, improve or modify the odor properties of aperfuming composition or of a perfumed article, which method comprisesadding to said composition or article an effective amount of at least acompound of formula (I). By “use of a compound of formula (I)” it has tobe understood here also the use of any composition containing a compound(I) and which can be advantageously employed in perfumery industry.

Said compositions, which in fact can be advantageously employed asperfuming ingredients, are also an object of the present invention.

Therefore, another object of the present invention is a perfumingcomposition comprising:

-   i) as perfuming ingredient, at least one invention's compound as    defined above;-   ii) at least one ingredient selected from the group consisting of a    perfumery carrier and a perfumery base; and-   iii) optionally at least one perfumery adjuvant.

By “perfumery carrier” we mean here a material which is practicallyneutral from a perfumery point of view, i.e. that does not significantlyalter the organoleptic properties of perfuming ingredients. Said carriermay be a liquid or a solid.

As liquid carrier one may cite, as non-limiting examples, an emulsifyingsystem, i.e. a solvent and a surfactant system, or a solvent commonlyused in perfumery. A detailed description of the nature and type ofsolvents commonly used in perfumery cannot be exhaustive. However, onecan cite as non-limiting example solvents such as dipropyleneglycol,diethyl phthalate, isopropyl myristate, benzyl benzoate,2-(2-ethoxyethoxy)-1-ethanol or ethyl citrate, which are the mostcommonly used. For the compositions which comprise both a perfumerycarrier and a perfumery base, other suitable perfumery carriers thanthose previously specified, can be also ethanol, water/ethanol mixtures,limonene or other terpenes, isoparaffins such as those known under thetrademark Isopar® (origin: Exxon Chemical) or glycol ethers and glycolether esters such as those known under the trademark Dowanol® (origin:Dow Chemical Company).

As solid carrier one may cite, as non-limiting examples, absorbing gumsor polymers, or yet encapsulating materials. Examples of such materialsmay comprise wall-forming and plasticizing materials, such as mono, di-or trisaccharides, natural or modified starches, hydrocolloids,cellulose derivatives, polyvinyl acetates, polyvinylalcohols, proteinsor pectins, or yet the materials cited in reference texts such as H.Scherz, Hydrokolloids: Stabilisatoren, Dickungs- and Geliermittel inLebensmittel, Band 2 der Schriftenreihe Lebensmittelchemie,Lebensmittelqualität, Behr's VerlagGmbH & Co., Hamburg, 1996. Theencapsulation is a well known process to a person skilled in the art,and may be performed, for instance, using techniques such asspray-drying, agglomeration or yet extrusion; or consists of a coatingencapsulation, including coacervation and complex coacervationtechniques.

By “perfumery base” we mean here a composition comprising at least oneperfuming co-ingredient.

Said perfuming co-ingredient is not of formula (I). Moreover, by“perfuming co-ingredient” it is meant here a compound, which is used ina perfuming preparation or a composition to impart a hedonic effect. Inother words such a co-ingredient, to be considered as being a perfumingone, must be recognized by a person skilled in the art as being able toimpart or modify in a positive or pleasant way the odor of acomposition, and not just as having an odor.

The nature and type of the perfuming co-ingredients present in the basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to intended use orapplication and the desired organoleptic effect. In general terms, theseperfuming co-ingredients belong to chemical classes as varied asalcohols, lactones, aldehydes, ketones, esters, ethers, acetates,nitriles, terpenoids, nitrogenous or sulphurous heterocyclic compoundsand essential oils, and said perfuming co-ingredients can be of naturalor synthetic origin. Many of these co-ingredients are in any case listedin reference texts such as the book by S. Arctander, Perfume and FlavorChemicals, 1969, Montclair, N.J., USA, or its more recent versions, orin other works of a similar nature, as well as in the abundant patentliterature in the field of perfumery. It is also understood that saidco-ingredients may also be compounds known to release in a controlledmanner various types of perfuming compounds.

According to any one of the above embodiments of the invention, and inparticular when the invention's compound is a 4,8-cyclododecadien-1-onemixture as defined above, at least one of said perfuming co-ingredientis a musk odorant. In particular said perfuming composition comprises:

-   i) as perfuming ingredient, at least one invention's compound as    defined above;-   ii) at least one perfuming co-ingredient having a woody and/or musk    character; and-   iii) optionally at least one perfumery adjuvant.

In particular said perfuming co-ingredient having a musk character canbe selected amongst Exaltolide® (pentadecanolide; origin: Firmenich SA,Geneva, Switzerland), Habanolide® (pentadecenolide; origin: FirmenichSA, Geneva, Switzerland), Romandolide®((1S,1′R)-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxycarbonyl]methylpropanoate; origin: Firmenich SA, Geneva, Switzerland), Helvetolide®((1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropylpropanoate; origin: Firmenich SA, Geneva, Switzerland).

Indeed in such a case, it has been noticed that in such composition, theinvention's compounds boost or impart an astonishing and cleannitro-musk and earthy effect, producing thus a synergetic effect in thedirection of Tonalide((5,6,7,8-tetrahydro-3,5,5,6,8,8-hexamethyl-2-naphtyl)-1-ethanone;origin: Givaudan SA, Vernier, Switzerland).

By “perfumery adjuvant” we mean here an ingredient capable of impartingadditional added benefit such as a color, a particular light resistance,chemical stability, etc. A detailed description of the nature and typeof adjuvant commonly used in perfuming bases cannot be exhaustive, butit has to be mentioned that said ingredients are well known to a personskilled in the art.

An invention's composition consisting of at least one compound offormula (I) and at least one perfumery carrier represents a particularembodiment of the invention as well as a perfuming compositioncomprising at least one compound of formula (I), at least one perfumerycarrier, at least one perfumery base, and optionally at least oneperfumery adjuvant.

It is useful to mention here that the possibility to have, in thecompositions mentioned above, more than one compound of formula (I) isimportant as it enables the perfumer to prepare accords, perfumes,possessing the odor tonality of various compounds of the invention,creating thus new tools for his work.

For the sake of clarity, it is also understood that any mixtureresulting directly from a chemical synthesis, e.g. a reaction mediumwithout an adequate purification, in which the compound of the inventionwould be involved as a starting, intermediate or end-product could notbe considered as a perfuming composition according to the invention asfar as said mixture does not provide the inventive compound in asuitable form for perfumery. Thus, unpurified reaction mixtures aregenerally excluded from the present invention unless otherwisespecified.

Furthermore, the invention's compound can also be advantageously used inall the fields of modern perfumery, i.e. fine or functional perfumery,to positively impart or modify the odor of a consumer product into whichsaid compound (I) is added. Consequently, a perfuming consumer productwhich comprises:

-   i) as perfuming ingredient, at least one compound of formula (I), as    defined above; and-   ii) a perfumery consumer base;    is also an object of the present invention.

The invention's compound can be added as such or as part of aninvention's perfuming composition.

For the sake of clarity, it has to be mentioned that by “perfumingconsumer product” it is meant a consumer product which is expected todeliver at least a perfuming effect, in other words it is a perfumedconsumer product. For the sake of clarity, it has to be mentioned thatby “perfumery consumer base” we mean here the functional formulation, aswell as optionally additional benefit agents, corresponding to aconsumer product which is compatible with perfuming ingredients and isexpected to deliver a pleasant odor to the surface to which it isapplied (e.g. skin, hair, textile, or home surface). In other words, aperfuming consumer product according to the invention comprises thefunctional formulation, as well as optionally additional benefit agents,corresponding to the desired consumer product, e.g. a detergent or anair freshener, and an olfactive effective amount of at least oneinvention's compound.

The nature and type of the constituents of the perfumery consumer basedo not warrant a more detailed description here, which in any case wouldnot be exhaustive, the skilled person being able to select them on thebasis of his general knowledge and according to the nature and thedesired effect of said product.

Non-limiting examples of suitable perfumery consumer base can be aperfume, such as a fine perfume, a cologne or an after-shave lotion; afabric care product, such as a liquid or solid detergent, a fabricsoftener, a fabric refresher, an ironing water, a paper, or a bleach; abody-care product, such as a hair care product (e.g. a shampoo, acoloring preparation or a hair spray), a cosmetic preparation (e.g. avanishing cream or a deodorant or antiperspirant), or a skin-careproduct (e.g. a perfumed soap, shower or bath mousse, oil or gel, or ahygiene product); an air care product, such as an air freshener or a“ready to use” powdered air freshener; or a home care product, such as awipe, a dish detergent or hard-surface detergent.

Some of the above-mentioned consumer product bases may represent anaggressive medium for the invention's compound, so that it may benecessary to protect the latter from premature decomposition, forexample by encapsulation or by chemically bounding it to anotherchemical which is suitable to release the invention's ingredient upon asuitable external stimulus, such as an enzyme, light, heat or a changeof pH.

The proportions in which the compounds according to the invention can beincorporated into the various aforementioned articles or compositionsvary within a wide range of values. These values are dependent on thenature of the article to be perfumed and on the desired organolepticeffect as well as the nature of the co-ingredients in a given base whenthe compounds according to the invention are mixed with perfumingco-ingredients, solvents or additives commonly used in the art.

For example, in the case of perfuming compositions, typicalconcentrations are in the order of 0.001% to 20% by weight, or evenmore, of the compounds of the invention based on the weight of thecomposition into which they are incorporated. Concentrations lower thanthese, such as in the order of 0.1% to 10% by weight, can be used whenthese compounds are incorporated into perfumed articles, percentagebeing relative to the weight of the article.

The invention's compounds can be prepared according to the literaturefor the ketone or standard methods known in the art as describedherein-below.

EXAMPLES

The invention will now be described in further detail by way of thefollowing examples, wherein the abbreviations have the usual meaning inthe art, the temperatures are indicated in degrees centigrade (° C.);the NMR spectral data were recorded in CDCl₃ (if not stated otherwise)with a 360 or 400 MHz machine for ¹H and ¹³C, the chemical shifts 6 areindicated in ppm with respect to TMS as standard, the coupling constantsJ are expressed in Hz.

Example 1 Synthesis of Compounds of Formula (I) 1. Preparation of(E,E)-4,8-cyclododecadien-1-one(4E,8E)-13-oxabicyclo[10.1.0]trideca-4,8-diene

To a mechanically stirred solution of E,E,E-1,4,8-cyclododecatriene(22.5 g, 139 mmol, available commercially from Alfa Aesar) in methylenechloride (200 ml) was added sodium bicarbonate (12 g, 139 mmol). Themixture was cooled to 0° C. and m-chloroperbenzoic acid (24 g, 166 mmol)was added in small portions over 2 hours. The reaction mixture wasstirred at 0° C. for 1 hour, then allowed to warm to ambienttemperature. Filtration, washing with sodium hydrogen sulphate (2portions of 30 ml 10% aq. solution) and distillation of the methylenechloride solvent yielded the crude product. The crude product wasdissolved in MTBE, washed with aqueous NaHCO₃, water and brine. Thesolvent was evaporated and the product (31.3 g; 30% starting material,63% monoepoxide; 7% diepoxide) purified by distillation. The puremonoepoxide crystallised spontaneously (yield=79% taking into accountrecovered substrate).

¹H-NMR: 1.08-1.20 (m, 2H); 1.80-1.94 (m, 2H); 2.02-2.18 (m, 4H);2.18-2.34 (m, 4H); 2.50-2.55 (d, 2H); 4.98-5.24 (m, 4H); 5.39-5.48 (m,1H).

¹³C NMR: 29.5 (t), 31.6 (t), 31.8 (t), 61.4 (d), 129.9 (d), 131.8 (d).

(E,E)-4,8-cyclododecadien-1-one

A mixture of lithium iodide (25 mg, 0.19 mmol) and the monoepoxideobtained above (1.05 g, 5.89 mmol) was heated to 200° C. After a fewminutes, the brown reaction mixture was cooled to ambient temperature,mixed with aqueous sodium bicarbonate and extracted with MTBE. Washingwith water, and brine, evaporation of the solvent and bulb to bulbdistillation (Kugelrohr oven, 0.2 mbar, 90° C.) yielded the targetketone (0.8 g; 97% pure, yield=74%).

¹H-NMR: 1.15-1.24 (m, 2H); 1.95-2.08 (m, 6H); 2.24-2.43 (m, 6H);5.00-5.18 (m, 4H).

¹³C NMR: 18.9 (t), 28.9 (t), 32.0 (t), 32.2 (t), 33.1 (t), 41.5 (t),42.9 (t), 128.9 (d), 130.9 (d), 131.4 (d), 133.1 (d), 210.7 (s);

2. Preparation of a Mixture of Isomers Containing the(E,Z)-4,8-cyclododecadien-1-one, (Z,E)-4,8-cyclododecadien-1-one the(E,E)-4,8-cyclododecadien-1-one isomers

To a mechanically stirred solution of (E,E)-4,8-cyclododecadien-1-one(10 g, 56 mmol) in n-propanol (50 ml) was added concentrated nitric acid(0.19 g, 60% aqueous). The mixture was heated to about 100° C. (reflux).After 7 hours of heating, an additional amount of concentrated nitricacid (0.05 g) was added and reflux continued for 16 hours. An additionalamount of concentrated nitric acid (0.05 g) was added and the mixturewas refluxed for another 44 hours. The solvent was evaporated and thecrude material (10.3 g) bulb to bulb distilled (Kugelrohr oven, 0.1mbar, 90° C.). The yellow distillate (8.7 g, yield=87%) was washed withNaOH (5% aqueous) followed by brine, then redistilled (Vigreuxdistillation 0.2 mbar at 63° C.). The composition of the colorlessdistillate was 64% 4,8-E,E isomer; 23% 4-E, 8-Z isomer and 12% 4-Z,8-Eisomer.

The individual isomers were separated by careful distillation using aFischer Spaltrohr™ column (vide infra).

Various mixtures with different ratios of each stereoisomers can beobtained by admixing the pure compounds.

a) The pure (4E,8Z) isomer (99%):

Separated by Fischer Spaltrohr™ distillation, 0.3 mbar, bp. 56.5° C.The compound was further purified by recrystallisation from cold (−30°C.) pentane. Mp=5.2° C.Odor: woody, earthy, cardamon

¹H-NMR: 1.65-1.75 (m, 2H); 1.95-2.05 (m, 6H); 2.30-2.50 (m, 6H);5.15-5.35 (m, 4H).

¹³C NMR: 21.4 (t), 24.7 (t), 27.4 (t), 28.7 (t), 31.5 (t), 40.5 (t),40.7 (t), 127.8 (d), 129.7 (d), 131.0 (d), 131.9 (d), 211.8 (s);

b) The pure (4Z,8E) isomer (96%):

Prepared by Fischer Spaltrohr™ distillation, 0.27 mbar, bp. 56.6° C.Odor: woody, earthy, weakly cardamon

¹H-NMR: 1.60-1.65 (m, 2H); 1.98-2.13 (m, 6H); 2.28-2.42 (m, 4H);2.45-2.51 (m, 2H); 5.08-5.23 (m, 2H); 5.28-5.33 (m, 1H); 5.39-5.48 (m,1H).

¹³C NMR: 19.6 (t), 24.0 (t), 27.5 (t), 31.0 (t), 31.7 (t), 40.5 (t),43.1 (t), 129.9 (d), 129.9 (d), 130.0 (d), 131.3 (d), 211.2 (s);

Each single isomer can also be obtained as described above in section 1by using the corresponding stereoisomer of the 1,4,8-cyclododecatriene.

3. Preparation of a Mixture Containing the Various (Z,E) and (E,E)Isomers of 12-methylcyclododeca-4,8-dienone and2-methylcyclododeca-4,8-dienone Preparation of a Mixture Containing E,Zand E,E Isomers of 2-methylcyclododeca-4,8-dienone and12-methylcyclododeca-4,8-dienone

To a cold (−70° C.) mechanically stirred mixture of diisopropylamine(12.07 g, 119 mmol) and THF (100 ml) under argon was added by syringe asolution of butyl lithium (70 ml, 1.6 molar in hexane). The mixture wasallowed to warm up to 0° C., kept at this temperature for 30 min andthen cooled down to −68°. Cyclododeca-4,8-dienone (20.1 g, 113 mmol; E,Zisomer mixture) was dissolved in THF (50 ml) and slowly added over 1 h.The mixture was allowed to warm to 0° C., then again cooled down to−72°. Methyl iodide (15.99 g, 113 mmol) was dissolved in THF (15 ml) andslowly added over 1 h. The mixture was allowed to warm to 20° C. andkept at this temperature overnight. Workup (reverse hydrolysis withice/aqueous HCl, extraction with MTBE, washing with water, then brine,distillation of the solvent) followed by bulb to bulb distillation(Kugelrohr oven, 0.21 mbar, 70° C.) gave an odoriferous mixture (20.7g). Flash-chromatography (heptane/ethyl acetate 98/2) using SiO₂ (345 g)allowed to separate the title mixture from remaining starting materialand dimethylated products.

The main isomers of 12-methylcyclododeca-4,8-dienone have been isolatedby repeated careful Fischer Spaltrohr™ vacuum distillation.

(4E,8E)-12-methylcyclododeca-4,8-dienone

Bp 45.0° C./0.1 mbar.

¹H-NMR: 1.08-1.12 (d, 3H); 1.22-1.31 (m, 1H); 1.77-2.12 (m, 6H);2.15-2.28 (m, 2H); 2.28-2.46 (m, 3H); 2.55-2.64 (m, 1H); 4.95-5.22 (m,4H).

¹³C NMR: 18.2 (q), 27.9 (t), 30.1 (t), 31.8 (t), 31.9 (t), 32.0 (t),40.3 (t), 46.5 (d), 129.9 (d), 129.9 (d), 132.4 (d), 132.5 (d), 213.7(s).

(4E,8Z)-12-methylcyclododeca-4,8-dienone

Bp 45.5° C./0.09 mbar.

¹H-NMR: 1.04-1.08 (d, 3H); 1.21-1.30 (m, 1H); 1.74-2.17 (m, 7H);2.20-2.32 (m, 2H); 2.42-2.52 (m, 1H); 2.60-2.74 (m, 2H); 5.20-5.35 (m,4H).

¹³C NMR: 17.8 (q), 24.2 (t), 27.3 (t), 27.9 (t), 31.2 (t), 31.6 (t),38.7 (t), 45.1 (d), 128.4 (d), 128.9 (d), 130.9 (d), 131.4 (d), 214.8(s).

(4Z,8E)-12-methylcyclododeca-4,8-dienone

Bp 39.5° C./0.05 mbar.

¹H-NMR: 1.05-1.10 (d, 3H); 1.25-1.35 (m, 1H); 1.75-2.15 (m, 7H);2.16-2.28 (m, 2H); 2.29-2.40 (m, 1H); 2.62-2.72 (m, 2H); 5.10-5.32 (m,3H); 5.44-5.52 (m, 1H).

¹³C NMR: 18.9 (q), 22.6 (t), 27.5 (t), 30.5 (t), 31.0 (t), 31.6 (t),41.6 (t), 44.3 (d), 129.5 (d), 130.2 (d), 130.4 (d), 131.0 (d), 214.6(s).

Example 2 Preparation of a Perfuming Composition

A perfuming composition for a man eau de Cologne was prepared byadmixing the following ingredients:

Parts by weight Ingredient 20 Carbinol acetate 20 Geranyl acetate 220Linalyl acetate 200 Bergamote essential oil 30 10%* Raspberry ketone 500Lemon essential oil 80 4-cyclohexyl-2-methyl-2-butanol ¹⁾ 120Exaltolide ® Total ²⁾ 80 Crystal moss 502-Methyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-penten- 1-ol ¹⁾ 8010%* Galbanum essential oil 100 Clove essential oil 40 Helvetolide ® ³⁾50 Hivernal ®⁴⁾ 200 Kephalis ⁵⁾ 200 Lavander essential oil 350 Lyral ®⁶⁾ 120 Marjoram essential oil 150 Nutmeg essential oil 100 Benzylsalicylate 200 Sandela ® ⁷⁾ 220 Sclareolate ® ⁸⁾ 202-Ethyl-4,4-dimethyl-1-cyclohexanone ¹⁾ 500 Vertofix ® Coeur ⁹⁾ 250(1S,2S,3S)-2,6,6-trimethyl-bicyclo[3.1.1] heptane-3-spiro-2′-cyclohexen-4′-on ¹⁾ 100 Ylang Extra 4000 *in dipropyleneglycol ¹⁾origin: Firmenich SA, Geneva, Switzerland ²⁾ pentadecanolide; origin:Firmenich SA, Geneva, Switzerland ³⁾(1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropylpropanoate; origin: Firmenich SA, Geneva, Switzerland⁴⁾3-(3,3/1,1-dimethyl-5-indanyl)propanal; origin: Firmenich SA, Geneva,Switzerland ⁵⁾ 4-(1-ethoxyethenyl)-3,3,5,5-tetramethyl-1-cyclohexanone;origin: Givaudan SA, Vernier, Switzerland ⁶⁾4/3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde; origin:International Flavors & Fragrances, USA ⁷⁾5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol; origin:Givaudan SA, Vernier, Switzerland ⁸⁾ propyl(S)-2-(1,1-dimethylpropoxy)propanoate; origin: Firmenich SA, Geneva,Switzerland ⁹⁾ methyl cedryl ketone; origin: International Flavors &Fragrances, USA

The addition of 100 parts by weight of (E,E)-4,8-cyclododecadien-1-oneto the above-described composition imparted to the latter a uniquetonality and reinforced the masculine aspects by pushing the woody notesand providing a nitro-musk twist to the musky notes.

The addition of 100 parts by weight of a mixture of diastereoisomerscontaining about 90% w/w of (E,Z)-4,8-cyclododecadien-1-one and(Z,E)-4,8-cyclododecadien-1-one diastereoisomers and about 5% w/w of the(E,E)-4,8-cyclododecadien-1-one diastereoisomer imparted to the abovecomposition an effect similar to the one imparted by(E,E)-4,8-cyclododecadien-1-one, but which was also more vetyver-earthyand reinforcing the green, aromatic/lavender tonalities.

Example 3 Preparation of a Perfuming Composition

A perfuming composition for a man eau de Cologne was prepared byadmixing the following ingredients:

Parts by weight Ingredient 10 Styrallyl acetate 70 Hexylcinnamicaldehyde 300 Bergamote essential oil 10 10%* Calone ® ¹⁾ 50 10%*Cis-3-Hexenol 50 Coriander essential oil 10 1,1-Dimethyl-2-phenylethylbutanoate 800 Hedione ® ²⁾ 500 Hedione ® HC ³⁾ 9003-(1,3-benzodioxol-5-yl)-2-méthylpropanal 10 10%* Isobutylquinoleine 4010%* Isojasmone 300 Jasmal ® ⁴⁾ 20 10%* 2,6-Dimethyl-5-heptanal ⁵⁾ 2010%* Nonenol 20 Trans-1-(2,2,6-triméthyl-1-cyclohexyl)-3-hexanol ⁵⁾ 30Oliban essential oil 5 Patchouli essential oil 620 Romandolide ® ⁶⁾ 20Rose essential oil 310 Benzyl salicylate 40 Cis-3-Hexenyl salicylate 15Cis-3-Hexenyl tiglate 50 10%* Gamma undecalactone 200 Vetyver Bourbon4400 *in dipropyleneglycol ¹⁾ 7-methyl-2H,4H-1,5-benzodioxepin-3-one;origin: Firmenich SA, Geneva, Switzerland ²⁾ methyl dihydrojasmonate;origin: Firmenich SA, Geneva, Switzerland ³⁾ methylcis-dihydrojasmonate; origin: Firmenich SA, Geneva, Switzerland ⁴⁾tetrahydro-3-pentyl-4(2h)-pyranyl acetate; origin: International Flavors& Fragrances, USA ⁵⁾ origin: Firmenich SA, Geneva, Switzerland ⁶⁾(1S,1′R)-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxycarbonyl]methylpropanoate; origin: Firmenich SA, Geneva, Switzerland

The addition of 200 parts by weight of (E,E)-4,8-cyclododecadien-1-oneto the above-described composition imparted to the latter a reinforcedvetyver aspect and imparted a woody/pin, musky twist which boosted themasculine connotation of the fragrance.

The addition of 100 parts by weight of a mixture of diastereoisomerscontaining about 90% w/w of (E,Z)-4,8-cyclododecadien-1-one and(Z,E)-4,8-cyclododecadien-1-one diastereoisomers and about 5% w/w of the(E,E)-4,8-cyclododecadien-1-one diastereoisomer imparted to the abovecomposition an effect clearly more rooty/earthy vetyver and slightlyless musky than the addition of (E,E)-4,8-cyclododecadien-1-one abovedescribed.

Example 4 Preparation of a Perfuming Composition

A perfuming composition of the musk type was prepared by admixing thefollowing ingredients:

Parts by weight Ingredient 308-Methoxy-2,6,6,8-tetramethyl-tricyclo[5.3.1.0(1,5)]undecane 5170Dipropylene glycol 300 Habanolide ® ²⁾ 600 Helvetolide ® ³⁾ 200Muscenone ™ Delta ⁴⁾ 6300 ¹⁾ pentadecenolide; origin: Firmenich SA,Geneva, Switzerland ²⁾(1S,1′R)-2-[1-(3′,3′-dimethyl-1′-cyclohexyl)ethoxy]-2-methylpropylpropanoate; origin: Firmenich SA, Geneva, Switzerland ³⁾3-methyl-(4/5)-cyclopentadecenone; origin: Firmenich SA, Geneva,Switzerland

The addition of 1000 parts by weight of (E,E)-4,8-cyclododecadien-1-oneto the above-described composition imparted to the latter an astonishingreminiscence of the nitro-musk notes.

The addition of 1000 parts by weight of a mixture of diastereoisomerscontaining about 90% w/w of (E,Z)-4,8-cyclododecadien-1-one and(Z,E)-4,8-cyclododecadien-1-one diastereoisomers and about 5% w/w of the(E,E)-4,8-cyclododecadien-1-one diastereoisomer boosted the earthyaspects, providing thus an astonishing reminiscence of the aromaticpolycyclic musks which are nowadays strongly limited in use.

1.-10. (canceled)
 11. A compound of formula (I)

wherein one R group is a hydrogen atom and the other is a hydrogen atomor a C₁₋₃ alkyl group, wherein the compound (I) is in the form of amixture of stereoisomers (4E,8E), (4Z,8E) and (4E,8Z), wherein the w/wratio of (4E,8E)/[(4Z,8E)+(4E,8Z)] is between 20/80 and 1/99, or between80/20 and 99.5/0.5.
 12. A method of use of a compound of formula (I) asperfuming ingredient

wherein one R group is a hydrogen atom and the other is a hydrogen atomor a C₁₋₃ alkyl group; and each carbon-carbon double bond of thecompound (I), independently of each other, can be in a configuration Zor E or a mixture thereof.
 13. The method of use of claim 12, whereinone R group is a hydrogen atom and the other is a hydrogen atom or amethyl or ethyl group.
 14. The method of use of claim 12, wherein thecompound (I) is in the form of a mixture of stereoisomers (4E,8E),(4Z,8E) and (4E,8Z), wherein the w/w ratio of (4E,8E)/[(4Z,8E)+(4E,8Z)]is between 20/80 and 1/99, or between 80/20 and 99.5/0.5.
 15. The methodof use of claim 12, wherein the compound (I) is(E,E)-4,8-cyclododecadien-1-one, (Z,E)-4,8-cyclododecadien-1-one,(E,Z)-4,8-cyclododecadien-1-one,(4E,8E)-12-methylcyclododeca-4,8-dienone,(4E,8Z)-12-methylcyclododeca-4,8-dienone,(4Z,8E)-12-methylcyclododeca-4,8-dienone,2-methylcyclododeca-4,8-dienone or a mixture thereof.
 16. A perfumingcomposition comprising: i) at least one compound of formula (I), asdefined in claim 12; ii) at least one ingredient selected from the groupconsisting of a perfumery carrier and a perfumery base; and iii)optionally at least one perfumery adjuvant.
 17. A perfuming compositionaccording to claim 16, wherein the perfumery base comprises at least oneperfuming co-ingredient having a woody and/or musk character.
 18. Aperfuming consumer product comprising: i) at least one compound offormula (I), as defined in claim 12; and ii) a perfumery consumer base.19. A perfuming consumer product according to claim 18, wherein theperfumery consumer base is a perfume, a fabric care product, a body-careproduct, an air care product or a home care product.
 20. A perfumingconsumer product according to claim 18, wherein the perfumery consumerbase is a fine perfume, a cologne, an after-shave lotion, a liquid orsolid detergent, a fabric softener, a fabric refresher, an ironingwater, a paper, a bleach, a shampoo, a coloring preparation, a hairspray, a vanishing cream, a deodorant or antiperspirant, a perfumedsoap, shower or bath mousse, oil or gel, a hygiene product, an airfreshener, a “ready to use” powdered air freshener, a wipe, a dishdetergent or hard-surface detergent.